Softener composition

ABSTRACT

A softener composition, which contains tri-long-chain alkyl quaternary ammonium salt that has been considered to be difficult to use as a softener base agent, and which can provide a softener composition that provides a sufficient softening performance, is provided with (A) a cationic surfactant comprising at least one selected from the group consisting of quaternary ammonium salts represented by the formulae (I), (II) or (III), wherein the ratio of quaternary ammonium salt represented by the formula (I) to the total amount of these salts exceeds 50 weight %, with the ratio thereof represented by (III) being set to not more than 10%, and (B) at least one nonionic surfactant. In this case, (A) may include tertiary amine.  
                 
 
     (wherein, R 1 , R 2 and R 3  represent long-chain alkyl groups, etc. having total carbon atoms of 8 to 40, which may be intersected by an ether group, an ester group or an amide group; R 4  represents an alkyl group, etc. having carbon atoms of 1 to 6, and X − represents an anionic group.)

FIELD OF THE INVENTION

[0001] The present invention relates to a preparation method ofquaternary ammonium salt that is desirably used as a softener baseagent, quaternary ammonium salt obtained through such a preparationmethod and a softener composition containing such salt that exhibitssuperior softness.

BACKGROUND OF THE INVENTION

[0002] In recent years, most of the products that are commerciallyavailable as the fiber-use softener have a composition containingquaternary ammonium salt having two long-chain alkyl groups in eachmolecule, as typically represented by di(long-chain alkyl)dimethylammonium chloride. However, the quaternary ammonium salt of this typehas a problem in which, when its residual substances after use aredischarged into the natural field, most of them are accumulated withoutbeing subjected to biodegradation.

[0003] In order to solve this problem, N-methyl-N,N-bis(long-chainalkanoyl oxyethyl)-N-(2-hydroxyethyl) ammonium methylsulfate or the likehas been introduced to the market as modified products. In comparisonwith the above-mentioned quaternary ammonium salt, this product hasbetter biodegradability.

[0004] N-methyl-N,N-bis(long-chain alkanoyl oxyethyl)-N-(2-hydroxyethyl)ammonium methylsulfate is prepared by esterifying triethanol amine usinga long-chain fatty acid and successively quaternizing this by dimethylsulfate. The reaction molar ratio of fatty acid to triethanol amine isnormally set to 1.8 to 2.1, and in this case, the ratio of diesterquaternary salt to the total amount of monoester quaternary salt,diester quaternary salt and triester quaternary salt is 43 to 47 weight%. The reaction molar ratio is set to 1.8 to 2.1 because at this time,the ratio of diester quaternary salt is maximized, and the reactionmolar ratio smaller than 1.8 or greater than 2.1 causes a reduction inthe ratio of diester quaternary salt, resulting in degradation in thesoftening performance. However, even when the reaction molar ratio isset within 1.8 to 2.1, it is not necessarily possible to provide asufficient softening property.

[0005] In order to solve the above-mentioned problem, W09742279 hasdisclosed quaternary ammonium salt in which the ratio of diesterquaternary salt is not less than 55 weight % with the ratio of triesterquaternary salt being set to not more than 25 weight %, and thepreparation method thereof. Although this product has an improvedsoftening performance, it has not been a satisfactory product.

[0006] Most of the other softener base agents have the di-long-chainalkyl quaternary ammonium salt structure, and with respect totri-long-chain alkyl quaternary ammonium salt, the application thereofas a softener base agent has not been proposed because of the reasonsthat more hydrophilic groups exist in comparison with lipophilic groupswith insufficient dispersing property to water with the result that thesoftening performance is not sufficiently exerted.

[0007] Moreover, such quaternary ammonium salt is prepared by allowingthe corresponding tertiary ammine to react with a quaternizing agent andat the time of the quaternizing reaction, alcohol solvents such asisopropyl alcohol and ethanol are generally used. However, alcohol basedsolvents have a low flash point which causes a risk of a fire, and alsohave inherent odor causing adverse effects on odor of the productscontaining these base agents, and these do not function as effectivecomponents for softening cloth and hair, etc., resulting in thecorresponding additional costs. However, without the application of sucha solvent, the melting point of quaternary ammonium salt becomes higher,resulting in another problem with handling.

[0008] The objective of the present invention is to provide a softenercomposition which contains tri-long-chain alkyl quaternary ammonium saltthat has been considered to be difficult to use as a softener baseagent, and which provides a sufficient softening performance.

[0009] EP-A675941 and WO97/42279 disclose a mixture of quaternaryammonium salts including 50% or more of a triester-having quaternaryammonium salt.

[0010] Wo01/32813 and JP-A 2001-131871 disclose a mixture of quaternaryammonium salts including 15 to 85% of a tri-ester-having quaternaryammonium salt, up to 40% of a di-ester-having quaternary ammonium saltand 15 to 85 of a mono-ester-having quaternary ammonium salt for a for asoftener. DE-A 1935499 discloses production of a tri-ester-havingquaternary ammonium for softener, in Example 2.

DISCLOSURE OF THE INVENTION

[0011] The objective of the present invention is to provide a softenercomposition that contains tri-long-chain alkyl quaternary ammonium saltand is excellent in softening property and biodegradability. Thiscomposition also has a good property in fish toxicity testing.

[0012] Therefore, the purpose of the present invention is also toprovide an efficient preparation method of a quaternary ammonium saltthat is excellent in softener base agent and have a goodbiodegradability.

[0013] The present invention provides a softener composition comprisingthe following components (A) and (B): (A): a cationic surfactantcomprising at least one selected from the group consisting of quaternaryammonium salts represented by the formulae (I), (II) or (III), whereinthe ratio of the quaternary ammonium salt represented by the formula (I)to the total amount of the quaternary ammonium salts represented by theformulae (I), (II) and (III) exceeds 50 weight % and the ratio of (III)to the sum total of (I), (II) and (III) is not more than 10%:

[0014] wherein R¹, R² and R³ represent a long-chain alkyl or alkenylgroup having the total carbon atoms of 8 to 40, which are the same as ordifferent from one another and may be intersected by an ether group, anester group or an amide group; R⁴ represents an alkyl group, an alkenylgroup or a hydroxy alkyl group, having 1 to 6 carbon atoms, plural R⁴ 'sbeing the same as or different from one another; and X⁻represents ananionic group, (B): a nonionic surfactant that is a compound representedby the following formula (IV):

R⁵COO—(AO)m—R⁶  (IV)

[0015] wherein, R⁵ represents an alkyl or alkenyl group having the totalcarbon atoms of 7 to 29, R⁶ represents an alkyl or alkenyl group having1 to 6 carbon atoms, A represents an alkylene group having 2 to 4 carbonatoms and m is a number of 1 to 40 on the average value and plural A'smay be the same as or different from one another.

[0016] Moreover, the present invention provides a softener compositioncomprising the following components (A′) and (B′): (A′): a cationicsurfactant comprising at least one selected from the group consisting ofquaternary ammonium salts represented by the formulae (I), (II) or (III)as defined in claim 1 and at least one selected from the groupconsisting of amines or salts thereof represented by the followingformulae (V), (VI) or (VII), where the ratio of the total mole number ofthe quaternary ammonium salts to the total molar number of amines or thesalts thereof is 99.9:0.1 to 70:30 and the ratio of the quaternaryammonium salts represented by the formula (I) to the total amount of thequaternary ammonium salts represented by the formulae (I), (II) and(III) exceeds 50 weight % and the ratio of (III) to the sum total of(I), (II) and (III) is not more than 10%:

[0017] wherein R¹, R^(2,) R³ and R⁴ are the same as described above),(B′): at least one nonionic surfactant selected from the groupconsisting of compounds represented by the formula (IV) as defined inclaim 1 and the following formulae (VIII) or (IX):

[0018] wherein, R⁷ represents an alkyl group, an alkenyl group or anacyl group, having carbon atoms of 8 to 22, A represents an alkylenegroup having 2 to 4 carbon atoms, n represents a number of 4 to 100 onthe average value, p and q are a number of 1 to 50 on the average value,being the same as or different from each other, and plural A's may bethe same as or different from one another.

[0019] The compounds having the formulae (VIII) and (IX) preferably havean HLB value of 9-17, more preferably 10-16.

[0020] The incorporation of the amine compounds (V), (VI) or (VII) or asalt thereof provides the resulting softener composition with a goodfeeling in touch of chemical fabric in addition to cotton fabric.

[0021] The ratio of the total mole number of the quaternary ammoniumsalts represented by the formulae (I), (II) and (III) to the total molenumber of amine salts represented by the formulae (V), (VI) or (VII) ispreferably 99:1 to 80:20.

[0022] R¹, R² and R³ are the same as or different from one anther andare preferably groups represented by the following formula (X) or (XI):

[0023] wherein, R⁸ and R⁹, which are the same as or different from eachother, represent an alkylene group having 2 to 6 carbon atoms and R¹⁰COrepresents a residual group resulting from a fatty acid having 8 to 30carbon atoms from which a hydroxyl group has been excluded.

[0024] The surfactant that is a compound represented by the formula (IV)has preferably an HLB of 9 to 17.

[0025] The blending ratio of component (A) to component (B) or component(A′) to component (B′) is preferably (A)/(B) or (A′)/(B′) by weight of{fraction (50/1)} to ½.

[0026] The blending ratio of component (A) or (A′) to the composition ispreferably 3 to 50 weight %.

[0027] The present invention provides a method of preparing any one ofthe above-mentioned softener compositions, comprising, first, comprisinga composition having the total amount of component (A) and component (B)or component (A′) and component (B′) of not less than 70 weight % andthen mixing it with water.

[0028] The present invention provides a method for preparing quaternaryammonium salts represented by the above-mentioned formula (I), (II) or(III), comprising reacting a tertiary amine represented by theabove-mentioned formula (V), (VI) or (VII) with a quaternizing agent toprepare a quaternary ammonium salt in at least one aprotic solventselected from the group consisting of ketone compounds, hydrocarboncompounds, heterocyclic compounds and compounds represented by thefollowing formula (XII):

R¹¹O—(AO)n—R¹²  (XII)

[0029] wherein R¹¹ and R², which are the same as or different from eachother, present alkyl groups, alkenyl groups or acyl groups, each havingcarbon atoms of 1 to 30, A represents an alkylene group having carbonatoms of 2 to 4, n represents a number of 1 to 40 on the average and nA's may be the same as or different from one another.

[0030] The aprotic solvent is preferably a compound represented by theformula (XII). Moreover, the compound represented by the formula (XII)is more preferably a compound represented by the formula (IV):

R⁵COO—(AO)m—R⁶  (IV)

[0031] wherein, R⁵, R⁶, A and m are defined as the same as describedabove.

DETAILED DESCRIPTION OF THE INVENTION

[0032] [(A) Component]

[0033] In order to provide sufficient softness, the component (A) of thecomposition of the present invention is designed so that the ratio ofquaternary ammonium salt represented by the formula (I) to the totalamount of quaternary ammonium salts represented by the formulae (I),(II) or (III) (hereinafter, respectively referred to as quaternaryammonium salts (I), (II), (III)) exceeds 50 weight %. More preferably,this value is set to not less than 85 or 90 weight %.

[0034] In the quaternary ammonium salts represented by theabove-mentioned formula (I), (II) or (III) constituting the component(A) (hereinafter, respectively referred to as quaternary ammonium salts(I), (II), (III)), with respect to R¹, R² and R³, groups represented bythe formula (X) or (XI) are preferably used.

[0035] In the formulae, R⁸ and R⁹, which are the same or different, arealkylene groups having carbon atoms of 2 to 6, more preferably, 2 to 3,and R¹⁰ CO represents a residual group resulting from a fatty acidhaving carbon atoms of 8 to 30, more preferably, 12 to 24, from which ahydroxyl group has been excluded.

[0036] With respect to R⁴, an alkyl group or a hydroxyalkyl group havingcarbon atoms of 1 to 3 is preferably used, and a methyl group, an ethylgroup or a hydroxyethyl group is more preferably used. With respect toX⁻, a halogen ion such as a chloride ion, or an alkylsulfate ion derivedfrom methylsulfate, ethylsulfate, etc. is preferably used.

[0037] The method for preparing the cationic surfactant that is thecomponent (A) of the present invention is not particularly limited. Forexample it can be prepared by quaternizing the product obtained byreacting an alkanol amine, an aminoalkyl amine or the like with an fattyacid or an ester thereof.

[0038] With respect to alkanol amine, aminoalkyl amine or the like,preferable examples include: triethanol amine, triisopropanol amine,N,N-bis (2-hydroxyethyl)propanediamine, and N,N-bis(2-hydroxypropyl)propanediamine. With respect to fatty acid and its ester, preferableexamples include: tallow fatty acid, hydrogenated tallow fatty acid,palm stearic acid, hydrogenated palm stearic acid or long-chain fattyacids of a mixture of two or more of these having carbon atoms of 8 to30, more preferably, 12 to 24, or lower alkyl esters thereof, or fatsand oils. With respect to the quaternizing agent, dimethylsulfate,diethylsulfate, methylchloride, etc. are preferably used.

[0039] As the reaction molar ratio of the fatty acid or its ester toalkanol amine, aminoalkyl amine, etc. is increased, the ratio ofquaternary ammonium salt (I) becomes greater; therefore, for example, inthe case when triethanol amine and tallow fatty acid are used asmaterials, the molar ratio of the fatty acid or its ester to triethanolamine is preferably set to not less than 2.7, more preferably, 2.7 to2.8.

[0040] With respect to quaternary ammonium salt (I), examples thereofinclude: N-methyl-N,N,N-tri(long-chain alkanoyloxyethyl) ammonium salt,N-methyl-N,N-di(long-chain alkanoyloxyethyl)-N-long-chainalkanoylaminopropyl ammonium salt, N-methyl-N,N-di(long-chainalkanoyloxyethyl)-N-long-chain alkanoylaminoethyl ammonium salt,N-methyl-N,N-di(long-chain alkanoyloxyethyl)-N-long-chain alkyl ammoniumsalt and N-methyl-tri-long-chain alkyl ammonium salt. Those having thelong-chain alkanoyloxy group and/or long-chain alkanoylamino group arepreferably used because of its superior biodegradability.

[0041] With respect to quaternary ammonium salts (I), (II), (III), thequaternary ammonium salts respectively represented by formulae (I-1),(I-2), (II-1), (II-2), (III-1) and (III-2) are more preferably used.

[0042] In the formulae, R⁴, R8, R⁹, R¹⁰CO and X^(—)are defined as thesame as described above.

[0043] [(B) Component]

[0044] With respect to alkylene oxide adducts of fatty acid ester ofcomponent (B), those having an HLB of 9 to 17, more preferably, 10 to16, are preferably used. Here, HLB is a value obtained from Griffinequation described in “W.C. Griffin, J.Soc. Cosmet. Chemists, 5, 249(1954).”

[0045] With respect to alkylene oxide adducts of fatty acid ester,examples thereof include those obtained by adding alkylene oxide tolower alkyl ester (with alkyl group having carbon atoms of 1 to 3) oflong-chain fatty acid having carbon atoms of 8 to 30, more preferably,12 to 24, such as tallow fatty acid, hydrogenated tallow fatty acid,palm stearic acid, hydrogenated palm stearic acid or mixtures of notless than two kinds selected from these, and those obtained by addingalkylene oxide to lower alcohol such as methanol, ethanol andisopropanol, and then esterifying these by using the above-mentionedlong-chain fatty acid or its lower alkyl ester With respect to thealkylene oxide to be added, ethylene oxide, propylene oxide, etc. arelisted, and ethylene oxide is more preferably used. The average addedmolar number of alkylene oxide is preferably set to 5 to 100, morepreferably, 10 to 30.

[0046] At least one kind selected from the group consisting of compoundsrepresented by the above-mentioned formula (VIII) or (IX), morepreferably, formula (VIII), is preferably used.

[0047] In formula (VIII) or (IX), R is preferably prepared as an alkylgroup, an alkenyl group or an acyl group having carbon atoms of 12 to20, more preferably, an alkyl group or an alkenyl group having carbonatoms of 16 to 18. A is preferably prepared as an ethylene group or apropylene group, more preferably, an ethylene group. Here, n ispreferably a number of 8 to 20, and p and q, which are the same ordifferent, are preferably set to 4 to 20.

[0048] [Softener Composition]

[0049] The blending ratio of the (a) component and (b) component of thesoftener composition of the present invention is preferably set to(a)/(b)(weight ratio)={fraction (50/1)} to ½, more preferably, {fraction(20/1)} to {fraction (1/1)}. Moreover, the amount of blend of (a)component in the composition is preferably set to 3 to 50 weight %, morepreferably, 4 to 30 weight %.

[0050] The (a) component and (b) component may be separatelyincorporated in a softener composition. It is more preferable to mix (a)and (b) with each other in advance to blend them simultaneously. Bydispersing these (a) and (b) components to water, it is possible to forma liquid softener.

[0051] The softener composition of the present invention is preferablyprepared by preliminarily obtaining a composition containing thecomponent (A) and component (B) the total amount of which accounts fornot less than 70 weight %, and then mixing this with water. Inparticular, it is preferable to mix the component (A) and component (B)in a completely dissolved state or molten state with water, and it ismore preferable to mix these with water having a temperature not lessthan the melting point of the mixture of the component (A) and component(B). The amount of water to be mixed is preferably set to such an amountas to finally set the total amount of the component (A) and component(B) in the softener composition to 3.1 to 60 weight %.

[0052] To the softener composition of the present invention, a nonionicsurfactant other than the component (B) may be added, in order toimprove the dispersing property and storage stabilizing property.Moreover, the following components may be added thereto on demand: fattyalcohol (more preferably, including carbon atoms of 8 to 24) or higherfatty acid (more preferably, including carbon atoms of 8 to 24) in orderto further improve the softness, lower alcohol such as ethanol orisopropanol, glycol, polyol and ethylene oxides and propylene oxides ofthese that are added as storage stabilizers, and inorganic salts, pHadjusting agents, hydrotropic agents, perfumes, antifoamers, pigments,etc.

[0053] The description of the above-mentioned compositions is alsoapplied to compositions containing the components (A′) and (B′).

[0054] In the present invention, the quaternizing reaction is preferablycarried out by adding an aprotic solvent using a tertiary amine andexecuting a quaternizing process using a quaternizing agent.

[0055] [Aprotic solvent]

[0056] The aprotic solvent used in the present invention is selectedfrom the group of compounds consisting of ketone compounds, hydrocarboncompounds, heterocyclic compounds and compounds represented by theformula (XII), and these may be liquid or solid matters at roomtemperature (25° C.) as long as they are liquids at the time of thequaternizing process. More specifically, examples thereof include ketonecompounds such as acetone and methylethyl ketone, hydrocarbon compoundssuch as pentane, hexane, heptane, octane, nonane and decane,heterocyclic compounds such as tetrahydrofuran and dioxane, andcompounds represented by the formula (XII); and compounds represented bythe formula (XII) are preferably used since they have superiormiscibility with water and also have preferable odor in the resultingquaternary ammonium salt.

[0057] In the formula (XII), the acyl group is preferably an acyl groupderived from a long-chain fatty acid having carbon atoms of 8 to 30,more preferably, 12 to 24, such as tallow fatty acid, hydrogenatedtallow fattyacid, palm stearic acid, hydrogenated palm stearic acid or amixture of two or more kinds selected from these. A is preferablyprepared as an ethylene group or a propylene group, more preferably, anethylene group. Here, n is preferably set to 1 to 30, more preferably, 5to 30.

[0058] With respect to the compound represented by the formula (XII),compounds represented by the following formulae (IV), (VIII) to (XVI)are listed, and compounds represented by the formula (IV) or (XIII) aremore preferably used, and most preferably, compounds represented by theformula (IV) are used, because of superior affinity to water, preferableodor generatiod by the resulting quaternary ammonium salt andcompatibility for use as a dispersant of the softener.

R⁵COO—(AO)m—R⁶  (IV)

R⁵COO—(AO)m—COR¹³  (XIII)

R¹⁴O—(AO)m—R¹⁵  (IV)

R¹⁶COO—(AO)m—R⁶  (XV)

R¹⁶COO—(AO)m—COR¹⁷  (XVI)

[0059] (wherein, R⁵ and R¹³, which are the same or different, representalkyl groups or alkenyl groups having carbon atoms of 7 to 29,preferably, 11 to 23, R⁶, R¹⁴ and R¹⁵, which are the same or different,represent alkyl groups or alkenyl groups having carbon atoms of 1 to 6,preferably, 1 to 5, R¹⁶ and R¹⁷, which are the same or different,represent alkyl groups or alkenyl groups having carbon atoms of 1 to 5,preferably, 1 to 4, and A and n are defined as the same as describedearlier).

[0060] [Tertiary amine]

[0061] In the tertiary amine (V), (IV), (VII), at least one of R¹, R²and R³ is R4; and with respect to R⁴, the groups respectivelyrepresented by the above-mentioned formula (X) or (XI) are preferablyused. The definition wherein is the same as described above.

[0062] Moreover, with respect to the alkyl group, the alkenyl group orthe hydroxyalkyl group having carbon atoms of 1 to 6, represented by R¹,R² and R³, an alkyl group or a hydroxyalkyl group having carbon atoms of1 to 3 is preferably used, and a methyl group, ethyl group orhydroxyethyl group is more preferably used.

[0063] With respect to the above-mentioned tertiary amines, as thecontent of the tri-long-chain alkyl tertiary amines in which all the R¹,R² and R³are R⁴ increases, the resulting quaternary ammonium salt hasgreater softness effects; therefore, the ratio of the tri-long-chainalkyl tertiary amines in the tertiary amines is preferably set to notless than 50 weight %, more preferably, not less than 85 weight %, mostpreferably, not less than 90 weight %. With respect to thetri-long-chain alkyl tertiary amines, those shown below are morepreferably used.

[0064] (R¹⁰CO is defined as the same as described above, r represents 2or 3.)

[0065] These tri-long-chain alkyl tertiary amines are obtained by, forexample, a method in which tri-alkanol amine such as tri-ethanol amineis subjected to a tri-esterification process, or a method in whichalkanol amines having an amino group within a molecule such asN-aminopropyl-N,N-hydroxyethylamine is subjected to a tri-acylationprocess. In this case, with respect to fatty acid or its ester to beused in the tri-esterification process or tri-acylation process,long-chain fatty acids having carbon atoms of 8 to 30, more preferably,12 to 24, such as tallow fatty acid, hydrogenated tallow fatty acid,palm stearic acid, hydrogenated palm stearic acid or a mixture of two ormore kinds selected from these, and its lower alkylester or fats andoils, may be used.

[0066] [Quaternizing reaction]

[0067] The aprotic solvent is preferably used at 5 to 90 weight %, morepreferably, 9 to 70 weight %, with respect to the tertiary amine. Withrespect to the quaternizing agents used in the quaternizing reaction,dimethylsulfate, diethylsulfate, methylchloride, etc. are listed. Thetemperature at the time of the quaternizing reaction is preferably setto 30 to 150° C., more preferably, 50 to 120° C.

[0068] In the case when, with respect to the aprotic solvent, a solventsuch as hexane that has low miscibility with water is used or when asolvent having odor such as acetone and tetrahydrofuran, is used, afterthe quaternizing process, the solvent is preferably evaporated away toform a lower alcohol solution such as isopropanol so as to be applied tothe softener. In the case when the compound represented by the formula(XII) is used as the aprotic solvent, the solution, as it is, withoutdistilling the solvent may be applied to the softener.

[0069] With respect to the quaternary ammonium salt obtained from thepresent invention, those having a ratio of not less than 50 weight %,more preferably, not less than 85 weight %, most preferably, not lessthan 90 weight %, of the tri-long-chain alkyl component in thequaternary ammonium salts, are preferably used.

EXAMPLES

[0070] In these examples, % represents weight reference unless otherwisedefined.

EXAMPLE 1

[0071] Triethanol amine (149 g) and 821 g of hydrogenated tallowfattyacid were used and subjected to an esterification reaction at 200°C. under nitrogen atmosphere for 10 hours to obtain N,N,N-tri(hydrogenated tallow alkanoyl oxyethyl) amine, and to this was furtheradded 458 g of hexane, and this was subjected to a quaternizing reactionby using 126 g of dimethyl sulfate at 70° C. for 10 hours. After thereaction, the solvent was evaporated therefrom under reduced pressure,and to this was then added 184 g of isopropanol to obtain an isopropanolsolution of quaternary ammonium salt. Table 1 shows the quaternizingratio and its composition.

[0072] Here, the quaternizing ratio and compositions were measured byusing an internal standard method based upon ¹H-NMR method by usingMERCURY 400 made by VARIAN.

EXAMPLE 2

[0073] N,N-di(hydroxy ethyl)amino propyl amine (162 g) and 821 g ofhydrogenated tallow fatty acid were used and subjected to anesterification reaction in the same manner as Example 1 to obtainN,N-di(hydrogenated tallow alkanoyl oxyethyl)-N-hydrogenated tallowankanoyl aminopropyl amine, and to this was added 465 g of hexane, andthis was subjected to a quaternizing reaction in the same manner asExample 1 by using 126 g of dimethyl sulfate, and after the solvent hadbeen evaporated therefrom, to this was then added 186 g of isopropanolto obtain an isopropanol solution of quaternary ammonium salt. Table 1shows the quaternizing ratio and its composition.

EXAMPLE 3

[0074] N,N-di(hydroxy ethyl)-N-hydrogenated tallow alkanoyl aminoethylamine (404 g) and 547 g of hydrogenated tallow fatty acid were usedand subjected to an esterification reaction in the same manner asExample 1 to obtain N,N-di(hydrogenated tallow alkanoyloxyethyl)-N-hydrogenated tallow alkanoyl aminoethyl amine, and to thiswas added 458 g of hexane, and this was subjected to a quaternizingreaction in the same manner as Example 1 by using 126 g of dimethylsulfate, and after the solvent had been evaporated therefrom, to thiswas then added 184 g of isopropanol to obtain an isopropanol solution ofquaternary ammonium salt. Table 1 shows the quaternizing ratio and itscomposition.

EXAMPLE 4

[0075] N,N-di (hydroxy ethyl)-N-hydrogenated tallow alkylamine (299 g)and 547 g of hydrogenated tallow fatty acid were used and subjected toan esterification reaction in the same manner as Example 1 to obtainN,N-di(hydrogenated tallow alkanoyl oxyethyl)-N-hydrogenated tallowalkylamine, and to this was added 405 g of hexane, and this wassubjected to a quaternizing reaction in the same manner as Example 1 byusing 126 g of dimethyl sulfate, and after the solvent had beenevaporated therefrom, to this was then added 165 g of isopropanol toobtain an isopropanol solution of quaternary ammonium salt. Table 1shows the quaternizing ratio and its composition.

EXAMPLE 5

[0076] The same processes as Example 1 were carried out except that 458g of acetone was used in place of hexane as a quaternizing solvent toobtain an isopropanol solution of quaternary ammonium salt. Table 1shows the quaternizing ratio and its composition.

EXAMPLE 6

[0077] The same processes as Example 1 were carried out except that 458g of tetrahydrofuran was used in place of hexane as a quaternizingsolvent to obtain an isopropanol solution of quaternary ammonium salt.Table 1 shows the quaternizing ratio and its composition.

EXAMPLE 7

[0078] Triethanol amine (149 g) and 821 g of hydrogenated tallow fattyacid were used and subjected to an esterification reaction at 200° C.under nitrogen atmosphere for 10 hours to obtain N,N,N-tri (hydrogenatedtallow alkanoyl oxyethyl) amine, and to this was further added 417 g ofethyleneoxide 12 mole adduct (HLB=14.0) of hydrogenated tallow fattyacid methyl ester as a quaternizing solvent, and this was subjected to aquaternizing reaction by using 126 g of dimethyl sulfate at 100° C. for10 hours to obtain a solution of hydrogenated tallow fatty acid methylester ethyleneoxide 12 mole adduct of quaternary ammonium salt. Table 1shows the quaternizing ratio and its composition.

EXAMPLE 8

[0079] The same processes as Example 7 were carried out except that 417g of ethylene glycol dimethylether was used in place of ethyleneoxide 12mole adduct of hydrogenated tallow fatty acid methyl ester as aquaternizing solvent to obtain an ethyleneglycol dimethylether solutionof quaternary ammonium salt. Table 1 shows the quaternizing ratio andits composition.

EXAMPLE 9

[0080] The same processes as Example 8 were carried out except that 417g of ethyleneglycol diacetate was used in place of ethylene glycoldimethylether as a quaternizing solvent to obtain an ethyleneglycoldiacetate solution of quaternary ammonium salt. Table 1 shows thequaternizing ratio and its composition.

EXAMPLE 10

[0081] N,N-di(hydroxyethyl)aminopropylamine (162 g) and 821 g ofhydrogenated tallow fatty acid were used and the same process as Example1 was carried out to obtain N,N-di(hydrogenated tallow alkanoyloxyethyl)-N-hydrogenated tallow alkanoyl aminopropyl amine, and to thiswas further added 422 g of ethyleneoxide 12 mole adduct (HLB=14.0) ofhydrogenated tallow fatty acid methyl ester as a quaternizing solvent,and this was subjected to a quaternizing reaction in the same manner asExample 7 to obtain a solution of hydrogenated tallow fatty acid methylester ethyleneoxide 12 mole adduct of quaternary ammonium salt. Table 1shows the quaternizing ratio and its composition.

EXAMPLE 11

[0082] N,N-di(hydroxy ethyl)-N-hydrogenated tallow alkanoyl aminoethylamine (404 g) and 547 g of hydrogenated tallow fatty acid were usedand subjected to an esterification reaction in the same manner asExample 1 to obtain N,N-di(hydrogenated tallow alkanoyloxyethyl)-N-hydrogenated tallow alkanoyl aminoethyl amine, and to thiswas further added 416 g of ethyleneoxide 12 mole adduct (HLB=14.0) ofhydrogenated tallow fatty acid methyl ester as a quaternizing solvent,and this was subjected to a quaternizing reaction in the same manner asExample 7 to obtain a solution of hydrogenated tallow fatty acid methylester ethyleneoxide 12 mole adduct of quaternary ammonium salt. Table 1shows the quaternizing ratio and its composition.

EXAMPLE 12

[0083] The same processes as Example 7 were carried out except that as aquaternizing solvent, 417 g of ethyleneoxide 15 mole adduct (HLB=14.9)of hydrogenated tallow fatty acid methyl hydrogenated ester was used inplace of ethyleneoxide 12 mole adduct of hydrogenated tallow fatty acidmethyl hydrogenated ester to obtain a solution of hydrogenated tallowfatty acid methyl hydrogenated ester ethyleneoxide 15 mole adduct ofquaternary ammonium salt. Table 1 shows the quaternizing ratio and itscomposition.

EXAMPLE 13

[0084] The same processes as Example 7 were carried out except that as aquaternizing solvent, 417 g of ethyleneoxide 18 mole adduct (HLB=15.5)of hydrogenated tallow fatty acid methyl hydrogenated ester was used inplace of ethyleneoxide 12 mole adduct of hydrogenated tallow fatty acidmethyl ester to obtain a solution of hydrogenated tallow fatty acidmethyl ester ethyleneoxide 18 mole adduct of quaternary ammonium salt.Table 1 shows the quaternizing ratio and its composition.

EXAMPLE 14

[0085] The same processes as Example 7 were carried out except that as aquaternizing solvent, 417 g of ethyleneoxide 21 mole adduct (HLB=16.0)of hydrogenated tallow fatty acid methyl hydrogenated ester was used inplace of ethyleneoxide 12 mole adduct of hydrogenated tallow fatty acidmethyl hydrogenated ester to obtain a solution of hydrogenated tallowfatty acid methyl hydrogenated ester ethyleneoxide 21 mole adduct ofquaternary ammonium salt. Table 1 shows the quaternizing ratio and itscomposition.

EXAMPLE 15

[0086] The same processes as Example 7 were carried out except that as aquaternizing solvent, 417 g of ethyleneoxide 9 mole adduct (HLB=12.9) ofhydrogenated tallow fatty acid methyl hydrogenated ester was used inplace of ethyleneoxide 12 mole adduct of hydrogenated tallow fatty acidmethyl hydrogenated ester to obtain a solution of hydrogenated tallowfatty acid methyl hydrogenated ester ethyleneoxide 9 mole adduct ofquaternary ammonium salt. Table 1 shows the quaternizing ratio and itscomposition.

EXAMPLE 16

[0087] The same processes as Example 1 were carried out except that 815g of hydrogenated tallow fatty acid was used in place of hydrogenatedtallow fatty acid in Example 1 to obtain a softener composition. Table 1shows the quaternizing ratio and its composition.

EXAMPLE 17

[0088] The same processes as Example 1 were carried out except that amixture of 408 g of tallow fatty acid and 411 g of hydrogenated tallowfatty acid was used in place of hydrogenated tallow fatty acid inExample 1 to obtain a softener composition. Table 1 shows thequaternizing ratio and its composition.

EXAMPLES 18 to 23, 25, 26, 33, 34

[0089] The solution of quaternary ammonium salt obtained in each ofExamples 1 to 6 and Examples, 8, 9, 16 and 17 was taken in a manner soas to set the total of quaternary ammonium salt to 5 g, and this wasmixed with 2 g of stearyl alcohol ethyleneoxide 13 mole adduct(HLB=14.0), and after having been heated to 60° C., this was drippedinto water at 60° C. in a molten state to prepare 100 g of a softenercomposition. The softness of these softener compositions was evaluatedin the following methods. Table 2 shows the results of evaluation.

EXAMPLES 24, 27 to 32

[0090] The solution of quaternary ammonium salt obtained in each ofExamples 7, 10 to 15 was taken in a manner so as to set the total ofquaternary ammonium salt to 5 g, and after having been heated to 60° C.,this was dripped into water at 60° C. in a molten state to prepare 100 gof a softener composition. The softness of these softener compositionswas evaluated in the following methods. Table 2 shows the results ofevaluation.

COMPARATIVE EXAMPLE 1

[0091] Triethanol amine (149 g) and 547 g of hydrogenated tallow fattyacid were used and subjected to an esterification reaction at 200° C.under nitrogen atmosphere for 10 hours to obtain N,N-bis(hydrogenatedtallow alkanoyl oxyethyl)-N-(2-hydroxyethyl) amine, and the sameprocesses as Example 1 were carried out by using 184 g of isopropanol asa quaternizing solvent to obtain an isopropanol solution of quaternaryammonium salt. Table 1 shows the quaternizing ratio and its composition.

COMPARATIVE EXAMPLE 2

[0092] The same processes as Example 1 were carried out except that 184g of isopropanol was used in place of hexane as a quaternizing solventto obtain an isopropanol solution of quaternary ammonium salt. Table 1shows the quaternizing ratio and its composition.

COMPARATIVE EXAMPLE 3

[0093] Triethanol amine (149 g) and 547 g of hydrogenated tallow fattyacid were used and subjected to an esterification reaction at 200° C.under nitrogen atmosphere for 10 hours, and to this was added 139 g ofisopropanol, and this was subjected to a quaternizing reaction at 60° C.by using 126 g of dimethyl sulfate to obtain a propanol solution ofN-methyl-N,N-bis(hydrogenated tallow alkanoyloxyethyl)-N-(2-hydroxyethyl)ammonium methyl sulfate. It was foundthrough NMR measurements that this solution had a long-chain alkylquaternary ammonium salt content of 12%, a di-long-chain alkylquaternary ammonium salt content of 35% and mono-long-chain alkylquaternary ammonium salt content of 15%. The resulting isopropanolsolution was taken in a manner so as to set the total amount ofquaternary ammonium salt to 5 g, and this was mixed with 2 g ofethyleneoxide 12 mole adduct (HLB=14.0) of hydrogenated tallow fattyacid methyl ester, in the same manner as Example 1 to prepare 100 g ofsoftener composition.

COMPARATIVE EXAMPLE 4

[0094] Triethanol amine (149 g) and 547 g of hydrogenated tallow fattyacid were used and subjected to an esterification reaction at 200° C.under nitrogen atmosphere for 10 hours to obtain N,N-bis(hydrogenatedtallow alkanoyl oxyethyl)-N-(2-hydroxyethyl) amine, and the sameprocesses as Example 1 were carried out by using 330 g of hexane as aquaternizing solvent to obtain an isopropanol solution of quaternaryammonium salt. Table 1 shows the quaternizing ratio and its composition.

COMPARATIVE EXAMPLES 5 TO 8 (EVALUATION OF COMPOSITIONS OF COMPARATIVEEXAMPLES 1 TO 4)

[0095] The solution of quaternary ammonium salt obtained in each ofComparative Examples 1 to 4 was taken in a manner so as to set the totalof quaternary ammonium salt to 5 g, and this was mixed with 2 g ofstearyl alcohol ethyleneoxide 13 mole adduct (HLB=14.0), and afterhaving been heated to 60° C., this was dripped into water at 60° C. in amolten state to prepare 100 g of a softener composition. The softness ofthese softener compositions was evaluated in the following methods.Table 2 shows the results of evaluation.

[0096] <Evaluation Method of Softness>

[0097] (1) Processing Method

[0098] Commercial cotton towels (1 kg) were put into a washing machineof 15 liters, and washed 5 times in hard water of 3.5.DH by usingcommercial detergent Attack (made by Kao Corp., registered trade name),and then to this was put 25 mL of the above-mentioned dispersingsolution, and this was stirred for one minute at 25° C.

[0099] (2) Evaluation Method of Softness

[0100] The cloth, treated as described above, was dried and left stillfor 24 hours in a thermo-hygrostat of 25° C., 65% RH. Evaluation ofsoftness was made on the cloth. The evaluation was made by comparingeach pair of cloths using the cloth treated in Comparative Example 3 asa reference. The evaluation was carried out based upon the followingcriteria.

[0101] +2; softer than the reference

[0102] +1; slightly softer than the reference

[0103] 0; as soft as the reference

[0104] −1; slightly harder than the reference

[0105] −2; harder than the reference TABLE 1 Composition of quaternaryammonium salt solution (%) Quaternizing Tri-long- Di-long- Mono-long-ratio chain alkyl chain alkyl chain alkyl (%) component componentcomponent Solvent Example 1 95 67 11 0 15 Example 2 93 66 11 0 15Example 3 91 64 11 0 15 Example 4 90 64 10 0 15 Example 5 89 63 10 0 15Example 6 93 66 10 0 15 Example 7 97 63 9 0 27 Example 8 95 67 10 0 15Example 9 91 65 10 0 15 Example 10 95 57 10 0 28 Example 11 93 56 9 0 29Example 12 95 58 10 0 27 Example 13 93 57 9 0 27 Example 14 91 55 9 0 27Example 15 91 54 9 0 27 Example 16 94 66 11 0 15 Example 17 94 66 11 015 Comparative 80 12 35 15  15 Example 1 Comparative 65 46 7 0 15Example 2 Comparative 80 12 35 15  15 Example 3 Comparative 85 18 36 15 15 Example 4

[0106] TABLE 2 Softness evaluation results Cationic Nonionic Cottonsurfactant surfactant towel Acrylic jersey Example 18 Compound 1Compound 18 +2 +2 Example 19 Compound 2 Compound 18 +2 +2 Example 20Compound 3 Compound 18 +2 +2 Example 21 Compound 4 Compound 18 +2 +1Example 22 Compound 5 Compound 18 +2 +1 Example 23 Compound 6 Compound18 +2 +1 Example 24 Compound 7 Compound 19 +2 +1 Example 25 Compound 8Compound 18 +2 +1 Example 26 Compound 9 Compound 18 +1 +1 Example 27Compound 10 Compound 19 +2 +2 Example 28 Compound 11 Compound 19 +2 +2Example 29 Compound 12 Compound 20 +1  0 Example 30 Compound 13 Compound21 +1 +1 Example 31 Compound 14 Compound 22 +1 +1 Example 32 Compound 15Compound 23 +1 +1 Example 33 Compound 16 Compound 18 +1 +1 Example 34Compound 17 Compound 18 +2 +1 Comparative Compound of Compound 18  0  0Example 5 Comparative Example 5 Comparative Compound of Compound 18 −2−2 Example 6 Comparative Example 6 Comparative Compound of Compound 19 0  0 Example 7 Comparative Example 7 Comparative Compound of Compound18  1  0 Example 8 Comparative Example 8

[0107] Compound 18: 13 mole adduct of stearyl alcohol ethylene oxide

[0108] Compound 19: 12 mole ethylene oxide adduct of hydrogenated tallowfatty acid methyl ester

[0109] Compound 20: 15 mole ethylene oxide adduct of hydrogenated tallowfatty acid methyl ester

[0110] Compound 21: 18 mole ethylene oxide adduct of hydrogenated tallowfatty acid methyl ester

[0111] Compound 22: 21 mole ethylene oxide adduct of hydrogenated tallowfatty acid methyl ester

[0112] Compound 23: 9 mole ethylene oxide adduct of hydrogenated tallowfatty acid methyl ester

1. A softener composition comprising the following components (A) and(B): (A): a cationic surfactant comprising at least one selected fromthe group consisting of quaternary ammonium salts represented by theformulae (I), (II) or (III), wherein the ratio of the quaternaryammonium salt represented by the formula (I) to the total amount of thequaternary ammonium salts represented by the formulae (I), (II) and(III) exceeds 50 weight % and the ratio of (III) to the sum total of(I), (II) and (III) is not more than 10%:

wherein R¹, R² and R³ represent a long-chain alkyl or alkenyl grouphaving the total carbon atoms of 8 to 40, which are the same as ordifferent from one another and may be intersected by an ether group, anester group or an amide group; R⁴ represents an alkyl group, an alkenylgroup or a hydroxy alkyl group, having 1 to 6 carbon atoms, plural R⁴'sbeing the same as or different from one another; and X⁻represents ananionic group, (B): a nonionic surfactant that is a compound representedby the following formula (IV): R⁵COO—(AO)m—R⁶  (IV) wherein, R⁵represents an alkyl or alkenyl group having the total carbon atoms of 7to 29, R⁶ represents an alkyl or alkenyl group having 1 to 6 carbonatoms, A represents an alkylene group having 2 to 4 carbon atoms and mis a number of 1 to 40 on the average value and plural A's may be thesame as or different from one another.
 2. A softener compositioncomprising the following components (A′) and (B′): (A′): a cationicsurfactant comprising at least one selected from the group consisting ofquaternary ammonium salts represented by the formulae (I), (II) or (III)as defined in claim 1 and at least one selected from the groupconsisting of amines or salts thereof represented by the followingformulae (V), (VI) or (VII), where the ratio of the total mole number ofthe quaternary ammonium salts to the total molar number of amines or thesalts thereof is 99.9:0.1 to 70:30 and the ratio of the quaternaryammonium salts represented by the formula (I) to the total amount of thequaternary ammonium salts represented by the formulae (I), (II) and(III) exceeds 50 weight % and the ratio of (III) to the sum total of(I), (II) and (III) is not more than 10%:

(wherein R¹, R², R³ and R are the same as described above), (B′): atleast one nonionic surfactant selected from the group consisting ofcompounds represented by the formula (IV) as defined in claim 1 and thefollowing formulae (VIII) or (IX):

wherein, R⁷ represents an alkyl group, an alkenyl group or an acylgroup, having carbon atoms of 8 to 22, A represents an alkylene grouphaving 2 to 4 carbon atoms, n represents a number of 4 to 100 on theaverage value, p and q are a number of 1 to 50 on the average value,being the same as or different from each other, and plural A's may bethe same as or different from one another.
 3. The softener compositionaccording to claim 2, wherein the ratio of the total mole number of thequaternary ammonium salts represented by the formulae (I), (II) and(III) to the total mole number of the amine salts represented by theformulae (V) (VI) and (VII) is 99:1 to 80:20.
 4. The softenercomposition according to any one of claims 1 to 3, wherein R¹, R²andR³are the same as or different from one another and are groupsrepresented by the following formula (X) or (XI):

wherein R⁸ and R⁹ are the same as or different from each other andrepresent an alkylene group having 2 to 6 carbon atoms and R¹⁰COrepresents a residual group resulting from a fatty acid having 8 to 30carbon atoms from which a hydroxyl group has been excluded.
 5. Thesoftener composition according to any one of claims 1, 3 and 4, whereinsaid surfactant that is a compound represented by the formula (IV) hasan HLB of 9 to
 17. 6. The softener composition according to any one ofclaims 1 to 5, wherein the blending ratio of the component (A) to thecomponent (B) or the component (A′) to the component (B′) is (A)/(B) or(A′)/(B′) by weight of {fraction (50/1)} to ½.
 7. The softenercomposition according to any one of claims 1 to 6, wherein the blendingratio of the component (A) or (A′) to the composition is 3 to 50 weight%.
 8. A method of preparing the softener composition described in anyone of claims 1 to 7, comprising, first, preparing a composition havingthe total amount of the component (A) and the component (B) or thecomponent (A′) and the component (B′) of not less than 70 weight % andmixing it with water.
 9. A method of preparing quaternary ammonium saltsrepresented by the following formula (I), (II) or (III), reacting atertiary amine represented by the following formula (V), (VI) or (VII)with a quaternizing agent to prepare quaternary ammonium salts in atleast one aprotic solvent selected from the group consisting of ketonecompounds, hydrocarbon compounds, heterocyclic compounds and compoundsrepresented by the following formula (XII): R¹¹O—(AO)n—R¹²  (XII)wherein, R¹, R², R³, R⁴and X are the same as described above,

(wherein R¹, R², R³ and R⁴are the same as described above), (XII)wherein R¹¹ and R¹², which are the same as or different from each other,represent an alkyl group, an alkenyl group or an acyl groups, eachhaving 1 to 30 carbon atoms, A represents an alkylene group having 2 to4 carbon atoms, n represents a number of 1 to 40 in the average valueand n A's may be the same as or different from one another.
 10. Themethod according to claim 9, wherein said aprotic solvent is a compoundrepresented by the formula (XII).
 11. The method according to claim 10,wherein said compound represented by the formula (XII) is a compoundrepresented by the formula (IV): R⁶COO—(AO)n—R⁷  (IV) wherein R⁶, R⁷, Aand n are defined as the same as described above.